Process for breaking petroleum emulsions



Patented Feb. 20, 1 951 UNITED STATES ATENT OFFICE -rnoonssns FOR BREAKING PETROLEUM EMULSIONS No Drawing. Application April 22, 1949, Serial No. 89,138

This invention relates to processes or proce- Claims. (Cl. 252-342) type, and particularly petroleum emulsions. This i 3 application is a continuation-impart of our 00- pending application SerialNo. 751,616, filed May 31, 1947 (now abandoned) Attention is also directed to our co-pending application Serial No. 64,468, filed December 8, 194 8.

Complementary t0 the above aspect of the invention herein disclosed,in our companion invention concerned with the new chemical products or compounds used as the 4 demulsifying agents in said aforementioned processes or pro cedures, as well as the application of such chemical compounds, products, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds whi'ch'are' of outstanding value in demulsification. See our co-pending application Serial No. 89,139, filed April 22, 1949.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily'oil, emulsified oil, etc., "and which'comprise fine droplets of naturally-occurring waters or brines' dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of, the

emulsion.

It also provides aneconomical and rapid process for separating emulsions which. have been prepared under controlled conditions from min-, eral oil, such as crude oil andrelatively soft waters or weak ,brines. Controlled emulsification and subsequent demulsification under the condi, tions just mentioned areoi significant value in removing impurities, particularly inorganic salts, from pipeline oil. a

Demulsification as contemplated in the present applicationyincludes thepreventive step of comminglingthe demu lsi fienwith the aqueous component which would might subsequently become 'either phase of the emu-lsion in'the absence of such "precautionary measure. Similarly; such demulsifier maybejmixed with'the hydro ri QQm QE t-Ji. If f i 1B iefl .t e eaiifi r g a on t c n m with the breakihgcrre'solving of'petroleum'emulsions by means of certain esters which are, in turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated derivatives of certain resins hereinafter specified.

Thus, the present process is concerned with breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of an ester of a hydroxylated monocarboxy acid having less than 8 carbon atoms and hydrophile hydroxylated aliphatic synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) An alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and

(B) An oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, phenolaldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R1O)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ester as well as 3 the oxyalkylated resin in an equal weight of Xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volume of water.

For purpose of convenience what is said hereinafter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion 'of the immediately aforementioned derivative into a total or partial ster by reaction with hydroxyacetic acid or the like; and Part 4 will be concerned with the use of such esters as demulsifiers, as hereinafter described.

PART 1 February 16, 1948 (both now abandoned). Ina-' such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymer of the formula resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially aifect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde, on one hand, and a comparable product prepared from the same phenolic reactant and htptaldehyde on the other hand. The former, as shown in certain subsequent examples-sis ,a hard',.brittle} solid,==whereas, the latter is softand tacky, and-obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particuf-la rly benzaldehyde. 'The employment of furfural requires careful control, for the reason fural can-formvinyl condensations by virtue of R R n" R In such idealized representation 11." is a numeral varying from 1 to 13, or even more, provided the resin is fusible and'organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application B may have as many as 12 carbon atoms, as in the case of a resin obtained from a dodecylphenol. In the instant invention it 'may be first suitable to describe the alkylene oxides'employed as reactants, then the aldchydes, and finally the phenols, for the reasonthat the-latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more ex pensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self- "its unsaturated structure. The production of resinsfrom furfural for use in preparing reacand often with alkali metal carbonates. Useful aldeyhd'csfin addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2- ethylhexanal, 'ethylbutyraldehyde, heptaldehyde, and -benzaldehyde, furfural' and gly'oxal. It would appearthat-the-uSe'of glyoxal -should be avoided, due to the'fact'that-itis tetrafunctional. However, ourexperienc has been that, in resin manufacture and particularlyas described herein, apparently only one' oi-thealdehydic functions-enters into theresin-ification' reaction. The inability of the other-aldehydi function to enter into the reaction-istpresumably due to steric hindrance. Needless'to say; 'one'-canuse a mixture of"twoor"-morealdehydes; although usually this has-"no" advantage.

Resins of the k indwhichare used as intermediates in'this inventi'on'are obtained with the use of acid catalysts- "or-alkaline catalysts, or without the use of any "catalyst at all. Among the useful alkaline "catalysts are ammonia, amines, and quaternary ammonium bases. It is generally acceptedthat when ammonia and amines are employed as catalysts'they'enter into the condensatiori reaction, and in fact, may operate by initial combination with thealdehydic reactant. The compound he'xamethylenetetramine illustrates such a combination. In light of these variousr'eacti'ons, it'becomes diffi'cult to present any formula which would depict the structure of the various resin's'p'rior tobxyalkylation' More will be said subse uenuyas to the difference between the use of an alkaline catalyst and an acid catalystfeven' intheliise' of an alkaline catalyst there' is considerable evidence to indicate that the products are notidentical where differentbasic materials 'areemployed. '.'The basic materials employed include not only those previously enumerated," but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts 'of" strong bases and weak acids, such as sodium acetate, etc.

Suitable phenolic'reactants include the following: Para-tertiarybutylphenol; para-secondarybutylphenol; Iaara-teztiary-amylphenol; parasecondary amylphenol; 4 para-tertiary-hexylphenol; para-isooctylphenol; ortho-phenylphenol; p'ara-phenylphenol; -ortho-benzylpheno1; parabenzylphe'nol; and para-cyclohexylphenol, and the corresponding ortho-para-sub'stituted metacres'ols and 3,5-xyleno1s. Similarly, one may use the hydroxyl aerator para or ortho-nonyl'phenol, or a mixture, paraor ortho -decylphenol or a mixture, menthylphenol, or paraor ortho-dodecylphenol.

For convenience, the phenol has previously been referred to as monocyclic, in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically monocyclic is limited to the nucleus in which radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic, although the phenolic hydroxyl is, not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxyl group is directly" attached to a condensed or fused polycyclic structure, are excluded. This-matter, however, is clarified by the'following consideration. The phenols here in contemplated for reaction maybe indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl Substituted.

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5'methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

The manufacture of thermoplastic phenol-aldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known.

As has been previously pointed out, there is no I butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difiiculty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. 7 Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or suflicient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during-resiniiication. Structures which have been advancedtoexplamsuch increased use of aldehydes are the following:

Such structures may-lead 'to the production of cyclic polymers instead of linearpol'ymers. "For this reason, it has been previously pointed-out that, although linear, polymershave by far-the most important significance-the present invention does not exclude resins of "such' cyclic structures.

Sometimes conventional resinificatio'n "procedure is-employed using either acid or alkaline catalysts toproduce low-stageresins. Such'resins may be employed as such, or -may be altered or converted intohigh-stage resins, or in-any-event, into resins-of higher molecular weightby heating along with the employment of vacuum-s0 as to'split off wat-er or formaldehyde, or both. Generally 1 speaking, temperatures employed, particularlywith vacuum,-may be in the neighborhood :of 11 7 5 to 250 -'C.,-or thereabouts.

It may be Well to pom-tout, however, that the amount of formaldehyde used may and does usuallyaifect the length .of'zthe resin chain. .JIncreasing .the .amount of the .aldehyde, .such..as formaldehyde, .usually. .=increases the size .or .molecular weighttof :the polymer.

.In the heretoappendegd claimstheteis-specified, among other things, the .resinpolymer containing at least .3;;p enolic nuclei. finch minimum mole ular size is mos ccnveu ntly dete m ned s a rule b .cryscon "m thod .1 ben ene, -0 men he sui a e so ven stance. one 0f those ,ment-ioned eelsewhere ,herein as -,a z-solvent f r such resins. :As a matterof .fact. usi gth procedures herein described .or any conventional resinification procedure will yield ,1 products .usual- 1y having definitely in excess of .3 nuclei. In other words, a resinhavingan average-M4, 5 or 5 nuclei per unit is .apt 2170 be formed as .a minimum in resinification, except .under certain special conditions where dimerization .may ,occur.

However, if resins arepreparedat substantially higher temperatures, substituting .cymene, tetralin, etc, or some .other suitable solventwhich boils or reflexes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the timeof refluxing, usesia marked excess of formaldehydeor other aldehyde, then the average size .of .the resin, is apt .to .be' distinctly over the above values, for example, it may average i7 to 15 units. Sometimes'the expression low-stage resin orlow-stage intermediate is employed to mean astagehavingfior 7 units or.even less. flln'the appended clainiswe ha e u ed il w t t -meant? to 'kun ba d n averaee mole ul r w ht- The molecular weight determinations, of course-require that .the product be completely soluble in ithe ,particularsolvent selected as, .for instan'ce, .benzene. The molecular Weight determination of such solution may involve either the .treezing point .as in the cryoscopic method, or,=less-conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with thecryoscopic method, itis more apt to insure complete solubility. One such common -method to employ is that of'Menzies and Wright .(see J. Am. .Chem.Soc...l3, 2309and 2314 (1921) Any suitable method for determining molecular weights will serve, although almost any procedure adopted-has-inherent limitations. A good method I fordetermining themolecular Weights of resins,

especially solvent-soluble resins, is the .cr-yoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing 00., 1947) Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an Organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in vdetail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory "as those obtained employing acid catalysts. Sometimes a combination of-both typeset catalystsis used in different stages of "resinification. Resins so obtained "are also perfectly satisfactory.

In numerous instances the higher :molecular weight resins, i. e., those "referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a-modest amount or even perhapsno low polymer, yet it is almost certain to produce .further polymerization. For instance, ,acid catalyzed resins obtained in the usual "manner and having a molecular weight indicatingthe'presenceof approximatelyl phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum. t

We have found that under the usual conditions of resinificati-on employing ;phenols of the kind here described, there is little or no tendency to form binuclear compounds, i. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where .the substituent has-4 ..or .5 ,carbon atoms. "Where the number-of carbon atoms in ,a .Substituent approximates the upper limit s ecifiedherein, there maY besome tendency to dimerization. The usual procedure to obtain ,a dimer invo ves .enormcuslyflars exces f l phenol, for in ance, .8 to 10. m l per ol f ald hyde. Subs tuted .dihydroxydip ny m nes bta ned ifrom substi uted phenols are no resins as 'thatterm used herein.

,nl heugh an conventio a pro edure Qrdinarily 'e nn q ed ma be .us d in the manufact re o it her in cont mplated r s ns. or io it a r. c es :may be pur hased .in he open market, we have found it particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfo-acid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be 7 understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxalkylation thereof. The phenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having I a solvent present during the resinifying stage" if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, part cularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, proply benzene, mesitylene, decalin (decahydronaphthalene), tetra in (tetrahydronaphthalene) ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations.

Theuse of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 /2% to 40% formaldehyde, is the preferred reactant. When such solvent is used it is advantageously added at the beginning of the resinification procedure or before the reaction has proceeded very far.

more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol. which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be suflicient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the more random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxvalky ation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinifica- The solvent can be removed afterwards by distion procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as partof resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example 1a of our Patent 2,499,370 granted March 7, 1950. If the resin so obtained is solventsoluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately to C. with addtion of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. The oxyethylation is advantageously conducted so as to require from a few minutes up to. 5 to hours. If the. product so obtained is solvent-soluble and self-dispersing or' emulsifiable, or has. emulsifying properties, the phenol is perfectly satisfactory from the'standpoint' of trifunctional phenol content. The solvent may be removed prior to the dispersibility or emulsifiability test; When a product becomes rubbery duringv oxyalkylation. due to the presence of a small amount of. trireactive phenol, as previoiusly mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as beingjhydrophile as herein specified. Increasing the size ofthe' aldehydic nucleus, for instance using heptaldehyde. instead of formaldehyde, in=- creases tolerance for trifunctional phenol.

The presence of a trifunotional or tetra-functional phenol (such as resorcinol or; bisphenol A) isapt to produce detectable cross-linkingjand insolubilization but will not necessarily do-so, especially if the proportion is small. Resinification involving d func'tion'al phenols only may also produce insolubilization, although this seems tobe an anomaly or. a contradiction of what is sometimes said in regard'to resinifica'tion reactions involving difunctional phenols only. This is presumably due to cross-linking. Thi appears to be contradictoryi to what one might expect in light of the theory of functionality in'resinification. Itistrue that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional' phenols are very apt to, and almost. invariably: do, yield solvent-soluble, fusible resins. However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there is'involved the matter of color, solubility in.oil,. etc. When resins of the same type are; manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxvalkylation, such criteria. of selection are no longer pertinent. Stated another way, one" may use more drastic conditions of resinificationthan those ordinarily employed to produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures,,longer time of reaction, subsequent reaction involving heat alone or in. combination with vacuum, etc. Therefore, one. is not only concerned with the resinification reactionswhich yield the bulk'of' ordinary resins from difunctional phenols but also and particularly with .the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now'understood or explainable to a greateror' lesser degree in light of a most recent investigation. Reference ismade to the researches of Zinke andhis coworkers; Hultzsch and his associates, and to von" Eulen and his co-workers, and others; As to a bibliography of'su'ch investigations, see Carswell, Phenoplast's, chapter 2-. These investigators limited" much of their work to reactions involving phenols having two or lessreactive hydrogen atoms. Much of what appears in these most recent and most up-to-date investigations is pertinent to the" present invention insofar that much of it is referring to resinification in volving difunctional phenols.

For the moment, it may be simpler-to consider a most typical type of fusible resin andiforget for the time that such resin, at least under certain circumstances, is' susceptible to further complications; Subsequently in the text it will bep'ointed out thatcross-linking or reaction with excess formaldehyde may take place even with one of" such most typical type resins. This point is made for'the reason that insolubles must be avoided inorder to obtain the products'herein contemplated for use as reactants.

The typical .type of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly differentiated from the Novolak type or resole type of resin: Unlike the resole type,.sucl1 typical type para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike" the Novolak type the additionof a further reactant, for" instance, more: aldehyde, does. not ordinarily alterfusibility of the difunctional phenol-aldehydetype resin; butsuch addition to a- Novolak causes cross-linkingyby'virtue of the available third functional position.

' What has. been. said immediately preceding is subject tom'odification in this respect: It is well known. for. example, that. difunctional phenols, for" instance, paratertia'ryamylphenol, and an aldehyde; particularly formaldehyde, may yield heat hardenable. resins, at least under certain conditions; as. for example. the use of two moles of formaldehyde to one of phenol,, along with an alkaline catalyst; This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by various'authorities'.

The intermediates herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or'the subsequent; stage of resin manufacture where. heat alone, or" heat and vacuum, are employed, or in the oxyalkylati'on procedure. In its simplest presentation. the rationale. of resinification involving formaldehyde, for example, and" a difunctional phenol wouldinot be expected to form cross-links. However, cross-linking sometimes occurs'and it may reach the objectionable' stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations asv herein indicated, there is not the slightest diificulty'inpreparinga very large number of resins. of various types and from various reactants, andlby means of different catalysts by different procedures, all of which are eminentl'y' suitable for the herein described purpose.

Now returning to the thought that cross-link ing can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin; manufacture there may be a potential cross-linking combination formed but actual cross=linking maynot take place until the subsequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be'related'or explained in terms of a theory of flaws,. or Lockerstellen; which is employed in explaining, flaw-forming groups due to the fact that a CHzol-l'radical and. H atom may not lie in the same plane in the manufacture of ordinaryphenol-aldehyde resins.

Secondly, the formationor absence of formation" of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly formaldehyde, insofar that a slight variat on may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is a possibility that under some drastic conditions cross-linking may take place through "formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as-acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be suficiently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously decribed. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydro- 14 phile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the resins can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of com panies and can be purchased in the open market; in the second place there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The intermediate resins used in producing the products used in accordance with the present invention are exemplified by Examples 1a through 103a of our Patent 2,499,370, granted March 7, 1950, and we refer to that patent for examples, with specific directions, for the preparation of suitable oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenol-aldehyde resins derived from difunctional phenols.

Previous reference has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of para-butylphenol and para-amylphenol, or a mixture of para-butylphenol and para-h'exylphenol, or parabutylphenol and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants.

PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-Jeta olefine oxide so as to render the product distinctly hydrophile in nature, as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. The olefine oxides employed are characterized by the fact that they contain not over substituted ethylene oxides.

may be, of course, considered as'ahydroxypropylene oxide and methyl glyc'ideas a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of 01' The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glyc-ide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surface-W active properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition issuch'as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. conjunction with the three more favorablealkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have beenattached to the resin molecule, oxyalkylation. may. be satisfactorilycontinued using the more favorable members of the class,

to produce the'desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives becauseof their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective thanpropylene oxide, and propylene oxide is more effective than butyleneoxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) ismore-effective than butylene oxide.

Since ethylene @QXidB is the cheapest .alkylene oxide available andgis reactivaits use is definitely advantageous, and especially in light of itshigh oxygen content. iPropylene oxide isless reactive than ethylene oxide, and butylene oxide .isdefinitely less reactive than propylene oxide. On'the other hand,,glycide may react. with almost explo- ,sive violenc and must be handled with extreme care.

The oxyalkylation of resins of the kind, from which the initial reactants usedin thepractice of the present'invention are preparedis advantageously catalyzed by the presenceof an alkali.

.Useful alkaline catalysts include soaps,-sodium acetate, sodium hydroxide, sodium methylate, 55

caustic potash, etc. The amount of alkaline catalyst usually is between 0.2 to 2%. .The temperature employed may vary from room tempera- .ture toaas high as 200 C. The. reactionmaybe conducted with or Without pressure, 1.. e.,.from zero pressure to approximately .200 or even 300 pounds gauge pressurezfipounds per squareinch) In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organicmaterials having reactive phenolic groups.

It may be necessary to allow for the acidity of a :resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if ,a nonvolatile strong acid such assulfuric acidis used to catalyze the resinification reaction, pre- I sumably after being converted into a sulfonic acid,

it may be necessary and is usually advantageous to add an amount ofalkali equal stoichiomet- .rically to such ,acidity.:.and. includeiadded alkali They I are usable in' 6 "over and above this amount as the alkaline catalyst.

It'is'advantageous'to conduct the oxyethylation in presence of an inert solvent such as xylene,

cymene, decalin, ethylene lycol diethylether, di-

ethyleneglycol diethylether, or the like, although with many resins, the oxalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the 10 final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

'If' a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating "agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to300 poundsalong with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent'su'ch as xylene can be eliminated Pin either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide,

.:for example, per phenolic nucleus, there is a dellnite'drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by idistillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in .thetusualzmanner with ethylene oxide or some *other suitable." reactant.

.cAnother procedure is*'to continue the reaction :'to:.completion.-with such solvent present and then do geliminatevthe: solvent byzdistillation in the cus- .tomarymanner;

.Another suitable procedure is to use'propylene oxideor butylene oxide as a solvent as well as a reactant in the-earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide, even though oxyalkylation is taking place to a greater'or lesser degree.

After. a solution has been obtained which repre- -:'sents the original-resin dissolved in propylene oxide or butylene oxide, or a mixture which includes-the \oxyalkylated product, ethylene oxide .isadded .to react with the liquid mass until hy- .drophile properties are obtained. Since ethylene oxide ismore reactive than propylene oxide or butylene oxide, the final product may contain some-unreacted propylene oxide or butylene oxide which .can. be, eliminated by volatilization or distillation in any suitable .manner.

Attention is 'directedto the fact that the resins .lierein.described m'usthe fusible or soluble in an-organic solvent. "Fusible resins invariably are ..soluhle in one or more organic solvents such as those mentioned elsewhere herein. It to'be em- ,phasizedyhowever, that the organic solvent em- 'ployedtoindicate or. assure that the resinrneets -.this.requirement need not be the one used in oxy" 1 a-lkylation. .Indeed,.sol-vents which are susceptible to oxyalkylat-ion are included in'this group of or- .-gan-ic. solvents. Examples of such solven teareal- 7o cohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which ..are-not susceptible to 'oxyalkylation, useful for the oxyalkylation step. In any event, organic solvent.-soluble;:resimcan.he finely powdered, :for

instance, to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and sub- 'jected to oxyalkylation. The fact that the resin is soluble in an organic solvent, or the fact that it is fusible, means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive nydroxyl groups and are oxyalkylation-susceptible.

Considerable of what is said immediately here inafter is concerned with ability to vary the'hydrophile properties of the hydroxylated intermediate rcactant from minimum hydrophile properties to maximum hydrophile properties.

Such properties, in turn, of course, are effected subsequently by the acid employed for estcrification and the quantitative nature of the esterification itself, i. e., Whether it is total or partial. It may be well, however, to point out what has been said elsewhere in regard to the hydroxylated intermediate reactants. See, for example, our copending applications Serial Nos. 8,730 and 8,731, both filed February 16, 194.8, andSerial No. 42,133, filed August 2, 1348, and Serial No. 42,134, filed August 2, 1948 (all four cases now abandoned). The reason is that the esterification, depending upon the acid selected, may vary the hydrophilehydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherently different from the two reactants from which the derivative ester is obtained.

Referring to the hydrophile hydroxylated intermediates, even more remarkable and equally difficult to explain, are the versatility and the utility of these compounds considered as chemical reactants as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product showsat least emulsifying properties or self-dispersion in colder even warm distilled water to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperaturesaid in reducing the viscosity of the soluteunder examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solutiontakes place to give a homogeneous phase as themixture cools. Such self-dispersion tests are conducted inthe absence of an insoluble solvent.

When the hydrophileehydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufficient togive ,a sol as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to 90 parts by weight of oxyalkylated derivatives and 50 to. 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water .type or the water-in-oil type (usually the former) but, in any event, is .due to. the. hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufficient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such sol or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.) Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixture, 1. e., containing a water-insoluble solvent, is at least semi-stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as polyhydric reactants, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are selfemulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with prod.- ucts of the type used herein, most efficacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably deter mined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surfaceactive emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion depending upon, the ratio of the two phases, degree of agitation, concentration of emulsifying agent,etc.

. The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount ofdistilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained fromvpara-tertiary butylphenol and formaldehyde (ratio 1 partphenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufiiciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as. to the presence or absence of hydrophile or surface-ace.

tive characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinso-luble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point Where self-emulsification begins, then,

it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xy1ene free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material tov emulsiiy, a r insoluble;solyentsuch asxylena It is to be emphasized; that hydrophile properties herein referred to, are such asthose exhibited. by in c'ipientl seIf-emuIsificatiOn or the presence of emulsifying properties and go. through the range of homogeneous dispersibility or admixture. with water even in presenceof, added water-insoluble solvent and minor proportions of common electrolytes. as occur in oilgfi'eld brines.

' Elsewhere, it is pointed outthat an emulsificationtest may beused' to determine ranges of surface-activityand' that such emulsification tests employ a xylene solution, Stated another way, it is really immaterialwhetliera xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has. been, said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene' oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes'obvious that there is a wide variation in the amountofj alkylene oxide. employed, as long as it is at least 2 moles per phenolic nucleus, for producing products usetul for the practice of this invention, Another variation is the molecular size of theresin chain resulting from reaction between the difunctionalpho ol andthe aldehyde such as formaldehyde; It is wellknown that the size and nature or structure of theresin polymer obtained varies somewhat with the conditions of reaction, theproportions;of reactants, the nature ofthe catalyst, etc.

Based on molecular weight determinations, most of the resins prepared a herein described, particularly-in the absence oi a secondary heatingstep, contain 3-to'6*or' 7 phenolic nuclei-with approximately-i' or-5' nucleias an average. More drastic" conditions of resinification yield resinsof greater chain length. Suchmore intensiveresinific'ation isa conventional-procedure and maybe-employed'if desired. Molecular weight, of

course, is measured" by any suitable procedure,

particularlyby cryoscopicmethods; butusing the same reactants and-using more drastic conditions of resinification one-usually finds that higher molecular weights are indicated-- by higher melting points-o-fthev resins-and '2; tendency to decreased solubility. See what has been said elsewhere herein in regard to a: secondary step involving theheating of: a resin with orwithout the use of vacuum.

We have previously pointed outthat either an alkaline .or :acidacatalyst advantageously used inpreparing the-resin... A- combination of catalystsis sometimes used in two. stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of asmallamountof .acid catalyst in a sec- 0nd stage. Itaisgenerally believed that even in thelpresence, of an alkaline catalyst; the number of molesofaldehyde, such asiormaldehyde, must bengreater thanthetmoles ofsphenol employed in order to introducezmethylol. groups in the intertimes the weight of the original resin.

, 21 we have been able to determine, such resins are free from m-ethylol groups. As a matter of fact,

it is probable that in acid-catalyzed resinifica- .7 equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in step-wise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation, the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance, a few minutes to 2 to 6 hours, but in some instances, requires as much as 8 to 24 hours. A useful temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in stepwise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent, if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent, as a rule, varies from 70% by weight of the original resin to as much as five or six In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise, addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved, and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols andsome of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at 110 to 165 C., as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or sub-surfaceactive range without examining them by reaction with a number of the typical acids herein described and subsequently examining the resultant for utility, either in demulsification, or in some other art or industry, as referredto elsewhere or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2% to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% 0f xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of a1- kylene oxide. However, if one does not even care to go to the trouble of calculating molecular Weights, one can simply arbitrarily prepare cornpounds containing ethylene oxide equivalent to about 50% to 75% by weight, for example 65% by weight, of the resin to be oxyethylated; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about 10 to 15 gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophilerhydror phobejr'ange'. llLthese tests, vas stated',.are intended. to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylati'on, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating, the hydrophile'. hydrophobe range;

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certaindeterminationsin order to make the quickest approach tov the appropriate oxyalkylation range. For instance, one shouldknow (a) the molecular size, indicating the number of phenolic units; (12) the'n'ature of the aldehydic residue,which is usually CH2; and (c) the nature of the substituent, which is usually butyLamyl, or phenyl. With such information one is in substantially the same position as if one had'personally made the resin prior to oxyethylation.

For instance, the molecular weight of'the internal structural units of the resin of the following over-simplified formula:

R R R (71.21 120.13, or even more) is given approximately by the formula: (M01.

wt. of phenol 2). plusmol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is iden-- tical with the recurring internal unit except that it has one extrahydrogen. The right-hand terminal unit lacks the methylene bridge element.

Using one internal unit of a resin as thebasic element, a resins molecular weight is given approximately by taking (11. plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the struc ture. shown, this calculation will bein error by several. per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes 1 to be more than satisfactory; Using'such an approximate weight, one need only introduce, for

example, two molal weights of ethylene oxide or' slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character.

Further oxyalkylation gives enhanced hydrophile character. Although we have prepared andtested a large number of oxyethylated products of the type described herein, we have found no instance where the use of less than 2 moles of ethylene. oxide per phenolic nucleus gave desirabl'e products.

Examples 1b through 181) of our said Patent 2,499,370 illustrate suitable oxyalkylated' resins for use in preparing the products usedin accordance with the presentinvention, and specifically, certain oxyalkylated products derived from I resins of Examples 1a through 103a-of saicl'patf ent, which are examples of suitable intermediates for. the. practice of the. present invention,. as do thetabl'eswhich appear. incolumns 51' through 56' ofisaidlpatent, andlrefer'ence ismade. thereto for these specific examples.

The resins, prior to-oxyalkylation, vary fromtacky,. viscousliquids to hard; high-melting sol-- Their. color Varies, from. alight. yellow: through amber, to a deep red or even almost ids.

black. In. themanu'f acture of resins, particularly hardresins, asthe reaction progresses the reaction mass frequently. goes-through a liquidstateto asub-resinous or. semi-resinous state, ofter char acterized'by. being tacky orsticky, to afinal complete resin. As the resin issubjected to oxya-lkylation these "same. physical changes tend to take place in reverse. If one starts with-a-solid-resin,

oxyalkylation tends to make ittacky or semiresinousl and. further oxyalkylationi makes the tackiness disappear and changes the product toa liquid. Thus, asthe resin-is oxyalkylated it decreases-in viscosity, that is; becomes moreliquid or: changes from a solidto aliquid, particularly whenitdsconverted to thewater-dispersible or waiter-soluble:- stage. The color of the oxya-lkylatedderivative is usually considerably lighter than .the' original-product from which it is made, varyingfroma pale straw color to an amber or reddishamber. The viscosity-usually varies from that of an1oi-l, likevcastor oil,to that of a thick viscous. sirup. Someproducts are waxy. The

presence of a-solvent, suchas 15% xylene or the cooling of theresin, then of'course the initial resin is-much lighter in color. Wehave employed some resins which initially are almost water-white and also; yield a lighter colored final product.

Actually, in consideringthe ratio of alkylene oxide: to-add, and wehave previously pointedou-tthatthis can be pro-determined using laboratory--tests,-it is ouractualpreference, from a practical standpoint, to. make tests on a small pilot plantscale. Our reasonfor so doing is that we make one run; andonlyione and that-we have a complete series which shows the progressive efiect of introducing. the oxyalkylating. agent,q for instance, theethyleneoxy radicals; Ou-rpreferred procedure is. as follows: We prepare a suitableresin, or'for-that matter, purchase it in the open market. We employ 8 pounds of resin and 4' pounds -of:xylene and place the resin and xylene in arsuitable autoclave with an open reflux-con We: prefer'to heat-and stir. until the so- Wehave pointed out that denser: lution, is' complete;

soft-resins, which are fluid or semi-fluid can be readily-prepared in various ways, such as the use ortho-hydroxyI-- of ortho-tertiary amylphenol, diph'enyl', ortho-d'e'cylphenol, or by the use of higherrmolecularweight aldehydes than formal dehy'de." If such resins are used, a solvent need notib'e "added; but may be'added as 'amatter of convenience-, or'for comparison, if desired; We then add a-catalyst} for instance, 2 of I caustic sod'a, in th'e form-of a- 20% to 30% solution, and removethe-water of-solution or formation; We

then shut ofi the reflux condenser and use the 7; equipment as an autoclave only, and-'oxyethylate asaaoov 25 until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We'prefer a temperature of about 150 C.

to 175 C. We also take samples at intermediate points, as indicated in the following table:

Pounds of Ethylene Percentages Oxide Added per SFpound Batch oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4. ounces, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight 50 as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, 1. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be suflicient to indicate hydrophile character or surface activity, 1. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or droppin pipette, or any other procedure for measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a. laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant 26 which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain cross-linking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as lone, to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period.

It may be wel to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethyation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to 15% of xylene. Further oxyalkylation, particular'y oxyethylation, may then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggestng that some marked change has taken place. One explanation of the above change r 2s is that the structural un'itindicated 'inthe -folverify that the resin is organic solvent-soluble. lowing way where 811 is a fairly large 'number, Such "solubility test merely characterizes the for instance, .to "20, decomposes and an resin. 'Theparticular solvent .usedin such test oxyalkyfatedresin representing 'a'lower degreeof 'may'not be suitablefor atmolecular weight-deteroxyethylation and a less soluble 'one,is generated mination and, likewise, the solvent used in deterand a cyclic polymer of ethylene oxide is promining molecular weight may not be suitable as duced, indicated thus: a solvent during oxyalkylation. For solution of 32 .4 HH HJJH 0 C2 1 i R O(C H4O)anH ,R Q(Cz 4Q)4nH C2\1|, O 1.

II 0H4Cz This tract, of course, presents no difficulty ior'the the oxyalkylated compounds, or their derivatives reason that oxyalkylation scan 'heconductediin a great variety of solvents may be employed, each instance stepwise, or ata gradual rate, and such as alcohols, ether alcohols, cresols, phenols, samples-takenat short intervals so as to arrive ketones, esters, etc., alone or with the addition at a point where optimum surface activity or of water. Some of these are mentioned herehydrophile character is obtained .if desired; ,lfor :after. We prefer the use of benzene or iii- ..products .for use as polyhydric reactants in the phenylamine as a solvent in making cryoscopic practice of this Zinvent Qn, this is not necessary measurements. The most satisfactory resins :are and, in fact, may be undesirable, i. .e.,reduc e the 'those which are soluble 'in xylene or the lilre, eificiency of the product. rather than those whichare soluble only in some We do not know to .what extent soxya'lky-lation other sowent containing elements other than produces uniform distribution in regard to :carbon and hydrogen, for instance, oxygen :or phenolic'hydroxyls present in the resin molecule. chlorine. Such solvents are usually polar, semi- In some instances, of course, such distribution polar, or slightly polar in nature compared with cannot be uniform :for the reason that we have -x-y lene, cymene, etc.

,not specified that the molecules of ethyleneoxide, Reference to cryoscopic measurement is confor example, be added in multiples of the units cerned with :the use of benzene or other suitable present in the resin vmolecule. This may be :compound as a solvent. Such method will show illustrated inthe following manner: that conventional resins obtained, for example,

Suppose the 'resinhappens'to have fivephenolic from para-tert'ary amylp'henol and formalde- .nucTei. If .a minimum of two moles of ethylene 4O 'hyde, in presence 'of an acid catalyst, will have oxide perphenolic nucleus 'are added, this would a molecular weight indicating 3, l4, 5 or some mean an addition of 10 moles of ethylene oxide, what greater number of "structural units per 'butsuppose that one added 11 moles of ethylene m'o'lecule. If more'drastic conditions of resiniiioxide, or 12,.or 13 or 14 moles; obviously, even cation are employed, -or "if such low-stage resin assuming the most uniform distributionpossible, is subjected to a vacuum distillation treatment, some of the polyethyleneoxyradicals would'conas previously described, one obtains a resin of tain 3 ethyleneoxy units and some would contain :a distinctly higher molecu'ar weight. Any .2. Therefore, it 'isimpossible to specifyuni'form moleculanweig'ht determination used, whether distribution in "regard to the entrance of the cryoscopicmeasurement or otherwise, other than ethylene oxide or other oxyal-kylat'ing agent. For the conventional cryoscopic oneemploying that matter, if one Were-to introduce'25moles of 'benzene, should be checked so as to insure that ethylene oxide there is no way to'be certain that it gives consistent values on such conventional all chains of ethyleneoxy units would have '5 resins as a control. Frequently all that is necesunits; there might be some having, for example, sary to make an approximation of the molecular 4 and 6 units, or for that matter 3 or 7 "units. weight range is to "make a comparison with the Nor is there any basis for assuming that the dimer obtained by chemical combination of two number of molecules of the-'oxyalkylating"agent moles of the -samephenol, and'one mole of the added to each of the molecules of the resin is same aldehyde under conditions to insure dimerthe same, or different. Thus, whereiformulaetare 6n 'ization. As to the preparation of such dimers given to illustrate or depict the toxyal kyl ated *from substituted phenols, see Carswell, Phenoproducts, distributions of radicals indicated are plasts, page 31. The increased viscosity, to be statistically taken. We have, however, inresinouscharacter, and decreased solubility, etc., eluded specific directions .and specifications in of the higher polymers in comparison with the regard to the total amount of ethylene oxide,

dimer, frequently are all that is required to or total amount of any other oxyalkylating agent,

establish that the resin contains 3 'or more structo .add. 'tural units'per'molecu'le.

In regard to solubility of the resins and the Ordinarily, the oxyallsylation is carried out in 'oxyalkylated compounds, and for that matter autoclaves'provided with'agitators or stirringdederivatives of the latter, the following should be vices. Wehave-foundthat the'speed oftheagitanoted. In oxyalkylation, any solvent employed 7O tioirmarkedlyinfluences the reaction time. In should be non-reactive to the allrylene oxide emsome cases, "the change from slow speed agitaployed. This limitation does not apply to solvents tion, for example, in 'a laboratory autoclave agiused in cryoscopic determinations for obvious tation wit-hastirrer operating at-a speedof-SO reasons. Attention is directed to the fact that to 200 R. P. M., to'high speed agitation, with the various organic solvents may be employed to 7 stirrer operating at 250 to 350R. -P. reduces the time required for oxyalkylation by about one-. half to two thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, i. e., an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described. particularly adapted for demulsification of water-in-oil emulsions, and for that matter, for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance, as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds, thus, not only should a variety of resins be prepared exhibiting a variety of oxyalkylations, particularly oxyethylations, but also a variety of derivatives. This can be done conveniently in light of what has been said previously. From a practical standpoint. using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene ox de is one to one, 1 to 5, 1 to 10, 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided the pressure of the ethylene oxide was sufficiently great to pass into the autoclave, or else we have used an arrangement, which, in essence. was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle. combined with the means for either weighing the cylinder, or measuring the ethylene oxide used volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five diilerent variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period.

30 Since the addition of ethylene oxide is invariably an exothermic reaction, Whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (b) amount of cooling water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature, and then if ethylene'oxide is added slowly, this temperature is maintained by cool- 1 ing water until the oxyethylation is complete.

ject the ethylene oxide, as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the manner described in Examples Nos. la through 103a of our said Patent 2.499370, but instead of being prepared on a laboratory scale they were prepared in 10 to l5-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blew-Knox Co., Pittsburgh, Pennsylvania, and completely described in their Bul etin No. 2087, iss ed in 1947. with specific reference to specification No. 71-3965.

For convenience, the resins referred to in the following tables are identified by reference to the example numbers in our said Patent 2,499,370, and it is understood that they simply represent pilot plant operations, rather than laboratorysize operations.

The solvent used in each instance was xylene. This solvent is particularly satisfactory, for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance one-half to one gallon, one can proceed through the entire molal stage of l to 1, to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 1041a. In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result, it was necessary in such instances to start with a new resin sample, in order to prepare sufiicient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were bypassed or ignored. This is illustrated in the tables, where, obviously, it shows that the starting mix was not removed from a previous sample.

Phenol for resin: Para-tertiary amylphenol Date, .Tuno 22,..1948

"32 Aldehyde for resin: Formaldehyde [Resin made in pilot plant size 'bate'hfapproximately 25poun'ds, corresponding to 3a of Patent 2,499,370 but this batch designated 10411.]

Mix Which is Mix Which Re- Starting'Mix fig figg of .Removed for mains as'Next .Sample Starter Max. Max. Time 11ljressure '{empegahrs Solubility Lbs Lbs. .Lbs Lbs. Lbs.. Lbs. Lbs Lbs Lbs. Lbs Lbs. Lbs. Sol- Res- 801- Res- Sol- Res- 801- Has vent in Eto went in vent in Eto vent in First Stage 7 'Resin'to ?E"nO i Molal Ratio 11:1. .14. 25 15.175 .0 14.25 15. Z5 4.0 53.35 3.65 -.1.0 10. 9 12.1 3. I80 150 $4 I Ex.No. 1046.-...-

Second Stage 5 Resin to EtO i T Molal 'Ratio 1:5. 10. 9 12:1 3.0 10. 9 12.1 15. 3. 77 4. 17 '5. 31 7. 13 7. 93 9. 94 158 ST EXJNQ. 105b I 1 "Third Stage Resin to 12130.--. 3 Molal Ratio 1:1() 7.13 .7593 9.04 7.13 7.93 19.69 0.29, 3.68 9. 04 3.84 4. 25 10.65 60 173 9% FS EX.'N0.100b

.Fourth Stage 7 Resin to EtO 1 Mola] Ratio 1: 15 3.84 4.25 10..65 3.84 4. 25 16.15 .204 2.21 8.55 1.80 2. 04 7.60 .220 160 11; RS Ex. No. l07b 5 Fifth Stage ReSiIr'toEtOH a Molal Ratio 1:20 1.80 2.04 7.150 1. 2.04 10.2 .150 ,{1 Q3 EX. N0. 108b I=Insoluble. ST Slight tendency toward 'beconiing soluble. FS Fairly soluble. -RS Readily soluble. QS Quite soluble.

.Date, June 18, 1948 Phenol for resin: Nonylphenol Aldehyde for 'resin: Formaldehyde [Resin madeiapilotplant size batch, approximately 25 pounds, corresponding'to 70a oi'Patent 2,499,370 but this batch designated 10911.]

v 7 Mix Whichis Mix Which Re- Starting "Mi-x fig figg of Removed [or mains as Next Sample Starter M Ma Time nljressure itiemy egihrs Solubility pans. :Lbs.-- i Lbs, libs. Lbs. Lbs. "Lbs." Lbs. um,

Sol- Res- Sol-I Res- "Sol- .Res-

Sol- Resv vent in vent in vent in went in First Stage Resin 'to EtO M0121 Ratio 1:1 0 15.0 515.20 T3 550- 5.0 1.0 10.0 10.0 2.0 50 1% ST .E-X..NO. 109b Second Stage 'Resin' to mom; Molal Retin l "10 2.0; 10 10 '9.-14 2.72 2.72 2.56 7. 27 7. 27 6. 86 100 147 2 DT N0. l10b.

Third Stage Fourth Stage Resin to EtO. I j r v Molal Ratio 1 3.15 3.15 5:95 "3.15 '3. 15 8:95 "1.05 1.05 2.95 2.10 2.10 6.00 220 174 2% S Ex.;-'No.i11'2b I Fifth Stage Resin to EtO 7 I M0121 Ratio 1 2.10 2.10 '65 00 2.110 2. 10 8.500 a---" d 220 183 VS .EX..No..113b... 1

S=Soluble.

ST=S]igl1t.tendeney toward solubility.

DT=Definite tendency toward solubility.

VS Very soluble.

Phenol for resin: Para-octylphenol Date, June 23, 24, 1948 [Resin made in pilot plant size batch, approximately pounds, corresponding to 8a of Patent 2,499,370 but this batch designated 114a.]

Aldehyde for resin: Formaldehyde Date, July 8-13, 1948 Phenol for resin: M enthylphenol SS Somewhat soluble.

Aldehyde for resin: Formaldehyde Mix Which is Mix Which Re- Starting Mix f g figg of Removed for mains as Next Sample tarter Max. Max. Time Pressu e Temp erahm Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol- Res- Sol- Res- Sol- Res- Sol- Resvent in vent in vent in vent in First Stage Rosin to Et0.- Molal Ratio 1 14.2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.75 11.1 12.4 2.5 150 1142 NS Ex. N0. 114b.-.

Second Stage Resin to EtO.. Molal Ratio 1:5.- 11.1 12.4 2.5 11.1 12.4 12.5 7.0 7.82 7.88 4.1 4. 58 4.62 171 34 SS Ex. No. b.

Third Stage Resin to EtO.

Molal Ratio 1:10- 6.64 7. 36 O 6.64 7.36 15.0 190 1% S Ex. N0. l16b----- Fourth Stage Resin to Eton Molal Ratio 1:15. 4. 40 4.9 0 4.4 4.9 14.8 400 160 94 VS Ex. No. 1175.--

Fifth Stage Resin to EtO. Molal Ratio 1:20 4.1 4.58 4.62 4.1 4.58 18. 59 260 172 $6 VS Ex. No. 1180.....

S= Soluble. N S==N 0t soluble. VS=Very soluble.

[Resm made in pilot plant size batch, approximately 25 pounds, corresponding to 69a of Patent 2,499,370 but this batch designated 1190.]

Mix Which is Mix Which Re- Starting Mix 522 of Removed for mains as Next Sample Starter Max. Max. Time Pressu 'e Temp era- Solubility gbls. abs. Lbs lbls. Ifibs. Lbs gbls. Ifibs. Lbq ge s. es. Lbs

oes- 0- es- 0- es- 0- esvent in Em ve'nt in Eto vent in Em vent in Eto First Stage Resin to EtO.. Molal Ratiol 13.65 16.35 0 13.65 16.35 3.0 9.55 11.45 2.1 4.1 4.9 0.9 60 1% NS Ex. No. 1190.....

Second Stage Resin to 'EtO Molal Ratiol 10 12 0 10 12 10.75 4.52 5.42 4.81 5.48 6.58 6.94 140 1912 S Ex. No. 1200-.-"

Third Stage Resin to EtO Molal Ratiol 5.48 6.58 5.94 5.48 6.58 10.85 90 160 $4 8 Ex. No. 1210"..-

Fourth Stage Fifth. Stage Resin to EtO.- Molal Ratio 1:20. 3.10 3.72 0.68 3.10 3.72 13. 320 VS Ex. N0. 123b..--

S=Soluble. NS-Not soluble. IE-Very soluble- Date, July 14-15, 1948 [Resin made in pilot p1aliit siz batch, appmkimatelybs ounds, "cofiesponding'to "2a 'r'P-atefit 2.4993'7Ubut' this batch fiesignatd 12 ml} Whib is Mix Which Re- Starting Mix at End of Removed fbr mains as Next Reactlon I Sample Starter Max Max. Pr'essni'e Te m'p era- 55 sfl'lblhty I 1b's.'sq. in. ture; O; Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Sol- Resd Sol- Res- Eto S91; Res- S91- Resvent in vent in vent in vent in First Stage Resin to EtO 4 M01211 Ratio 1 1 14. 45 15. 55 14. 45 15. 55 41-25 5.97 6138 1'. 75 8. 48 9. 17 2. 50 B0 150 M2 N3 Ex. No. 124b Second Stage Resin to EtO M01211 Ratio 1:5 8; 48 9. 17 2.50 8. 48 9. 17," 16. 0 5. 83 6. 32 11. 05 -2. 65 2385 4. 95 95 188 M; SS Ex. No. 125b Third Stage Resin to EtO I M f v Molal Ratio 1:10 4. 82 5. 18 O 4.82- 5. 18 14.25 400 188 PE S Ex. No. 1260.1...

Fourth Stage Resin to EtO., Molal Ratio 1:-1'5 3. 85 4. 0- 3. 85 4.15 1 7-. 0 120 180 VS Ex. N0. 127b- Fifth Stage Resin to EtO H Molal' Ratio 1 t 20- 2. 2. -4'. 2. 65 2.85 1-5. 45 80 170 ia VS Ex. No. 12811 i Date, August 12-13, 1948 [Resin Inadebn pilbt plant size balth, a'pifibiirnatelj 25 A dehyde r b"; resin;- "Prdwndldhyde T r Mix Which is M11 WhichRg- Starting Mix of Remo'x' 'ed for mains ars Next Sample Sta ter Max Max I lg l i 31111 59, So1ub111ty 1 r ts;sq.1n. ure,'. @31 i122: 8'25: i122: 31 "1122: ms vnt in Eto vent 1n Eto vent 'in Eto Win; in Eto First Stag ResintoEtO... V. I .1 M0131 Ratio 1 12. 8 17. 2 12. 8 17. 2 2. 75 4'. 25 I 5. 7 0595 8. 55 11. 50 1.80 $5; Not Soluble. Ex. No. 12%

Second Stage Resinto EtO. V I i Molal Ratio 1. 8:55 11. 50 1. 80 8. 55 '11. 50 9. 3 4. 78 6. 42 5.2 3. 77 5308 4:10 100 SOm'Wha't soluble- Resin to EtO l Molal Ratio 1 0- 3: 77 5. O8 "4. 10 3. 77 5. 08 13.1 100 182 F -S6lub18. EX. N0. 1310 Fourth Stage Resin to EtO MolaL Ratio 5. 2 7. 0 5. 2 7. 0 -17. 0 3. 10 4.17 -10.-13 2. 10 83 6. 87 200 182 M Very 50111519. EX. N0. 1321) Fifth Stag Resin to EtO. H Molal. Ratio 1:20. 2:10 2. 83 '6587 2.10 2-83 9.12 90 150 $4. V'ly 'solilbl Ex. No. 133!) i 4 Phenol for resin: Para-tertiaiy aniylphenol Date, August 27-31, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2.499.370 but this batch designated as 13411.]

38' Aldehyde for resin: Farfural Mix Which is Mix Which Re- Starting Mix figg figs of Removed [or mains as Next Sample Starter Max Max Time Pressu 'e Temp era- Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbq mm, Sol- Res- 801- Res- Sol- Res- Sol- Resvent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1' 11.2'18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 120 135" $6 Not soluble. Ex No.134b

7 Second Stage Resin to Et MolalRatiol 8.45 13.6 2.65 8.45 13.6 12.65 5.03 8.12 7.55 3.42 5.48 5.10 110 150 $4 Somewhat Ex No.135b soluble.

Third Stage Resin to EtO- Molal Ratio 1:10-- 4.5 8.0 4.5 8.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 180 163 $4 Soluble. Ex. No.136b

Fourth Stage Resin to EtO. Molal Ratio 1:15-- 3.42 5.48 5.10 3.42 5.48 15.10 180 188 k; Verysoluble. Ex. No. 137b..

Fifth Stage Resin to EtO. Molal Ratio1:20 2.05 3.65 6.60 2.05 3.6513.35 120 125 )4; verysoluble Ex. No. 13Sb Phenol for resin: M enthyl Aldehyde for resin: Furfural Date, Sept. 23-24, 1948 [Resin made on pilot size batch, approximately 25 pounds, corresponding to 89a of Patent 2,499,370 but this batch designated as 13911.]

Mix Which is Mix Which Re- Starting Mix fi g fi g of Removed for mains as Next 0 Sample Starter Max. Max. Time nlj -essu 'e 'ilemp ercahrs Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. um,

Lbs. s Lbs. Lbs. Lbs. Sol- Resi bol- Res- -So1- Res- 501- Res- ,vent in Eto vent in Eto vent in Eto vent in Eto First Stage I Resin to EtO. Molal Ratio 1:1 10.25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 150 6 Not soluble. Ex. No.139b Second Stage Resin to EtO Moial Ratio 1:5 7.6 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 177 }6 Somewhat Ex.No.140b 1 soluble.

Third Stage Resin to EtO- Molal Ratio 1:10-- 4.22 6.98 4.22 6.98 10.0 165 Soluble. Ex.No.141b

Fourth Stage Resin to EtO Molal Ratio 1:15-} 3.76 6.24 3.76 6.24 13.25 171 ,4 Verysoluble. Ex. No. 142!) Fifth Stage Resin to EtO MolalRati01:20 2.4 4.15 2.95 2.4 4.15 11.70 9! y. Verysoluble. Ex. No. 1431) V Phenol-.for-res'zlniPamml Aldehyde'for resin: wfural Date, October 7-8, 1948 [Resin made on pilot plant size batch. approximately 25 ponnds, corresponding to, 42a of Patent 2.499.370 with 206 parts by'weight oi commecial para-octylphenolreplacing 164 parts by weight of; papa-tertiary amylphenol but his bat h designated es1144a1 1 m. wii iciii sf z Miic Which Re- Starting Mix g fi of Removedsfor mains a's Next" Sample Starter Max. Max. Time 1 r r 7 AM Pressu re Temp era- Solubility Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. L'bs'. Lbs Sol- Res- Sol- Res'-' Sol-v R es- S01 Resvent in vent in vent m vent in First Stage Resin to EtO. M0121 Ratio1:1-- 12.1 18.6 12.1 18.6 3.0 6.38; 8.28 1 .34; 6. 72 10.-32 1.66. 80 150 M2 Insoluble. EX. N0. 1440"--- Second Stage Slight tend- Resin to EtO.... 1 ency t9- Molai Ratio'1:5- 9 14. 25 9.25 14:25 11.0 3173; 5. 73,: 4.44 5. 52 8,52 6.56; 100 177; 212. ward be.- Ex. N 0.. 14512. coming S019 uble. Third Stage Resin to EtO I v M0121 Ratio 1:10. 6.72 10.32 1.66 6.72 10.32 14.91 4', 9T; 7; 62 11 .0L- 1. 75 2,70 3. 90 85 182 )4 Feirly- S9111.- Ex. No. 146b ble- Fomth Stage Resin to EtO M0121 Ratio 1:15- 5.52 8.52 6.56 5. 52v 8. 52 19.81 I h s V A V 10,0 176 Read ly sol- Ex. No. 147b uble.

Fifth Stages Resin to EtO MolaI Ratio 1:20 1'. 75 2.70 3.90 1. 75 2, 70 8.4 a w 80 160 M Quite sell;- Ex.N0.148b bis.

Phenolfor res'im Rafira-phenyl Aldehyde for resin: Fwfural Date. October 11-13, 1948 [Resin made on pilot plant size batch,.approximate1y 25 pounds. correspondingrto 42 0fv Patent 2,499,370. with 170, parts by weight of commercial paraphenylphenol replacing164 parts by weignt of para-tertiary amylphenol but this batch designated as 14911.]

f Mix Whiehis. Mix Whic Starting Mix fig ggg of Removed for mains as Next Sample Starter Max Max Time I I Pressuge Temp erahrs. Solubility 1 5 s. i bs. Lbs 1 .5 3. Ibs. I ms. lfibs. Lbs 1 5 s.v gm. Lbs f 0 eso es-' es- 0 esv'ent in v Eto vent in Eto vent. in Eto vent in Eco First Stage- ResintoEtO.. U 1 Molal Ratio 1:1. 13 9 16.7 13.9 16.7 3.0 3.50 4. 25 0.80 10.35 12. 45 2.20 100 160 $1; Insoluble. Ex. No.149b

Second Stage Resin. 551310.-.. I 1. 1 7 islighti MolaI Ratio 1:5.. 10. 12. 2. 20 10. 35 12. 45 12.20 5.15 5.19 6. 0s 5. 20 s. 25 6.14 so 183 ye Ex. No. 150b b111ty. Third Stage Resin to.Et;O. I 1 Molal Ratio 1:10. 8 90 10. 7 8. 9O 10. 19. 0 5. 30. 6. 38 11. 32 3. 60 4. 32 7. 68 193 12 Fairly 5011).- Ex. No. 151b. ble.

Fourth Stage Resinto 1260.-.. d I Molal Ratio 1:15. 5. 20 6. 26 6. 14 5. 20 6. 26 16. 64- 171 3'6 Readily Spl- Ex. No. 152b u e.

Fifth Stage .Resin to-EtO V. s V 5 1 Molal Rati) 1:20- 3 60 4. 32 7.68 3.60 4. 32 15.68 Sample somewhat rubbery andgelat- 2,30 ,2 Ex. N 0. 153b... inous but fairly soluble 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF A HYDROXYLATED ALIPHATIC MONOCARBOXY ACID HAVING LESS THAN 8 CARBON ATOMS AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATTION PRODUCTS OF: (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, AND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE ORGANIC SOLVENT - SOLUBLE, WATER - INSOLUBLE PHENOLALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA: 